Process foe the conversion of heavy



Dec. 24, 1946. E. HENE 2,412,983

PROCESS -FOR THE CONVERSION OF HEAVY HYDROCARBON LIQUID I Fi'led June17, 1943 2 Sheets-Sheet 2 Attorney Patented Dec. 24, 1946 7 PROCESS FORTHE CONVERSION OF HEAVY HYDROCARBON LIQUID Emil Hene, London, EnglandApplication June 17, 1943, Serial No. 491,190 In Great Britain April 14,1942 1 Claim. 1

This invention is concerned with improvements in or relating to the heattreatment of petroleum and like hydrocarbon products and/or hydrocarbonproducts obtained from the liquefaction or heat treatment of coal andthe like and t the production therefrom of other products.

In my application Serial No. 347,146, filed July 24, 1940, I havedescribed a process for the treatment of heavy residua and distillatesso as to obtain from them hydrocarbon products boiling mainly in the gasoil range with a minimum production of gasoline, gas and coke, whereinthe oil is very rapidly heated by being sprayed or dripped on to thesurface of a body composed of porous lumps, such as coke, heated to atemperature of from 400-600 C., the rate of feed and distribution of theoil and the size of the lumps being such that only a thin film of oil isformed on any lump at any instant of time, the vapours formed beingrapidly withdrawn. In that process the hydrocarbons are recovered asvapours, most of which are condensed into liquid oils, and no liquidresiduum remains.

In a later application Serial No. 481,923, filed April 5, 1943, I haveshown that under certain conditions the efiect of heat on petroleumproducts or alternatively the speed of the reaction or the response ofthe charging stock to the treatment can be greatly increased by theaddition of a small quantity of one or more catalysts or acceleratorsbelonging to the fifth periodic group of elements. For example, asdescribed in said application 481,923, I may use as the catalyst some ofthe catalyst-containing distillate obtained from a previous run with thesame catalyst I or catalysts. The use of these substances enables thethroughput to be increased, and also increases the paraffinicity of thehydrocarbons produced, whilst tending to decrease the formation of gas.

Continuing my investigations on processes of the kinds described in thesaid prior applications, I found and described in my Britishspecification No. 31/42 and in my corresponding United Statesapplication Serial No. 487,323, filed May 1'7, 1943, that by selectingcharging stocks in which paraffinic bodies did not predominate such forexample as cracked residua, and by operating the process at atemperature of from 400460 C. which constitutes the lower portion of therange covered in my application Serial No. 347,146 it is possible tomodify the nature of the resulting product and to produce in the mainnot ordinary gas oils, but oils of lubricating properties together withsome jellies and resinous products.

As a result of further investigations relating to the processesdescribed in my said earlier appli-' cations, it has now been found thatthe reaction passes through one or more intermediate stages, there beinga tendency for some of the hydrocarbons to increase in saturation,probably owing to a re-arrangement of large molecules or by reaction ofmolecules with one another or by a variety of changes which are oftenaccompanied by the formation of small quantities of products of a lowerboiling range. It has further been found that when the charging stockconsists, wholly or partly of heavy residua, either cracked oruncracked, the first or one of the first of these intermediate stagesresults in the formation of products which cannot be distilled withoutdecomposition under the conditions of the reaction, and which thusdecompose with the formation, in the main, of hydrocarbons, gas andcoke, unless they are rapidly removed in the liquid phase from thesphere of the reaction.

It has been found that these products comprise very valuablehydrocarbons such as resinous products, lubricating oils includingdrying oils, jellies and the like and the present invention is concernedinter alia with the production and separation of such products, which,we have found, can be effected by carefully controlling the reaction andeither stopping it at a desired intermediate stage or removing the saidproducts from its sphere.

The most suitable temperature range for bringing about the surfacereaction is comparatively low, lying between 430 and 485 C., in the caseof petroleum products and although we do not desire to be limited by anytheoretical explanations it may be said that it appears probable thatunder the conditions of the process an actual conversion of productstakes place, whereby substances which are still of high molecular weightand of increased saturation are produced by inter-reaction of componentsof the hydrocarbon mixture partly at the expense of the more asphalticmaterial, the hydrogen to carbon ratio of which is more and more reduceduntil it becomes immiscible with the remainder of the material andsettles together with a part of the substances produced on the surfacewhere, being undistillable under the existing conditions, it isconverted into coke. If, however, the coking of this material isprevented by its removal from the reaction surface in liquid phase itwill be found to contain various valuable products of the initial stagesof the convertive reaction.

Accordingly the invention consists inter alia in a process for thetreatment of heavy petroleum residua and the like in which the materialis so sprayed, dripped or otherwise applied to a heated surface undersuch conditions of temperature that each particle of the liquid israpidly raised to the temperature at which, in addition to some vapours,liquid and non-distillable con-' version products are formed on thesurface, said vapours and said liquid conversion products being as faras possible rapidly removed, in the vapour and liquid phasesrespectively from the reaction sphere before any substantialdecomposition of said liquid conversion products takes place.

For the purpose of controlling the progress of the reaction, it isusually desirable to collect any distillate and the liquid conversionproducts in separate receivers, but these will not in general enable acomplete separation to be effected, and the contents of each receiverare liable to contain varying quantities of the material which shouldhave been collected in the other. In such cases and to facilitate asatisfactory separation and working-up of the products, the contents ofthe two receivers may be mixed and subjected to any suitable separationtreatment. Details of a preferred method of separation are given in theexamples.

Alternatively, a direct separation, which will in most cases bepreferable, can generally be carried out in a suitable large scaleplant, such for example as that illustrated in Figure 4. Where such amethod is adopted, the liquid phase product will generally containlittle, if any, light oil, so that it will not usually be necessary toremove such oi1 by distillation, thus avoiding heating it to a hightemperature, which might have undesired eifects.

The process can be carried out either with or without the aid ofcatalysts or accelerators as described in the stated prior applications,and besides collecting the valuable products referred to, any distillatefrom the surface reaction can of course be separately condensed andcollected whilst any gas and/ or coke which may be formed can likewisebe collected and used.

In the case of petroleum products the temperature will generally liebetween 430 and 485 C, whilst in the case of gas tars, pitches and thelike it may in some cases be desirable to use temperatures of over 500C. (see Example 9).

The necessary control of the reaction and removal from its sphere of theconverted liquid phase can be effected in various ways.

Thus, if for any given plant andcharging stock the temperature remainsconstant, the rate of throughput will control the contact time and therate of removal of the liquid phase from the hot surface, which liquidcan be collected as such, whilst distillate vapours can be separatelycollected. An inert or carrier gas'may be used to remove or to assist inthe removal of the liquid from the reaction sphere. Moreover, the heatcapacity of the plant and the rate of heat application can be selectedto assist in bringing about the necessary conditions.

The products obtained according to the invention may containhydrocarbons of more paraffinic character which in the higher boilingrange (above 400 C.), are often of the character of a petroleum jelly.These can be separated by solvents of the furfural type. Such aseparation might in many cases be desirable, as resins containing aconsiderable proportion of such products require a much'longer time fordrying especially without drying agents. But such more parafiinichydrocarbons are generally more volatile than the resins, and it istherefore possible, by eiiicient separation of the vapour phase andliquid phase products, to obtain a liquid phase product, which by simpletreatment with a solvent e. g. solvent naphtha, results in producing asolution of resins which can be used without further treatment.

The liquid phase product may also be used as such for coating, etc.

As a rule, the vapour phase products contain lighter resins, and thus afurther variation in the number of resins of difierent properties can beobtained.

If desired some oil might be left with the resins thus reducing theirsoftening points but such products will still give a hard film, as theseoils have drying properties.

The process may be carried out in any convenient apparatus or plantwhich provides a suitable contact 'or conversion surface, adapted to bemaintained at the desired and properly controlled temperature with meansfor feeding the charge in the desired small portions, rapidly removingthe liquid conversion products and collecting any distillate.

The optimum rate of feed for a given surface depends on the character ofthe charge and on the extent to which it is desired to carry theconversion and therefore the optimum conditions can readily bedetermined in any particular case by measuring the ratio of distillateto liquid undistilled conversion products and by ascertaining the extentto which the distillate contains hydrocarbons of a lower boiling rangethan would be produced by a straight distillation of the charge.

If the contact surface consists of lumps of suitable material, as forexample coke, I have found it to be desirable gently and regularly todisturb the surface, so as to prevent agglomeration. The lumps may ifdesired be removed either continuously or discontinuously from thereaction vessel, broken down to the desired size and recharged on to thetop of the layer, if necessary after heating to a higher temperaturethan that of the reaction, so as if necessary to accelerate the completecoking of any deposit.

We have found that in many cases a liquid contact o1- conversionsurface,as for example a surface of molten lead, can with advantage be used,

suitable means being of course provided for removing and collecting theliquid conversion products. The use of such a surface has the advantagesof combining increased rate of heat transmission and consequentincreased throughput with ease of control of contact time andtemperature.

A tendency exists to form a layer of coke which would interfere withheat transmission. It may therefore be advisable to remove itcontinuously or discontinuously.

A solid heated metal surface can also be used, but owing to the tendencyto coke formation, the

" heat conductivity will gradually decrease unless the cok is regularlyremoved from the surface.

The following examples of results obtained according to our improvedprocess are given by way of illustrations only, and to. facilitate abetter understanding of the invention.

EXAMPLE S Apparatus.'1he various experiments details of which are givenbelow were all carried out in one or other of two forms of apparatusillustrated in Figure 1-3 of the accompanying drawings in which:

Figure l is a sectional elevation of an experimental apparatus using abed of coke as contact surface,

Figure 2 is a sectional elevation of a different apparatus in which the.contact surface consists of molten metal, and a Figure 3 is a plan ofthe apparatus illustrated in Figure 2.

Figure 4 is a diagrammatic and partly sectional representation of oneform of plant suitable for continuous operation of the process on alarge scale.

Referring to Figure l, the experimental reaction vessel l was ofcircular cross-section, the diameter being 3" and the height 6". Thevessel I, which was constructed of iron, was fitted with a perforatedplate 2 on which was arranged a bed of lumps of coke 3 of approximatelyin average diameter, and with a rotatable lid 4, the downturned flangeof which dipped into a bath of molten lead 5, which surrounded thevessel l, and which was heated by a laterally disposed burner not shown,A funnel B for feeding the charge was centrally disposed in the lid 4,and was provided with a cock 1, the delivery end 8 being bent so that byrotation of the lid the charge could be spread over the periphery of thecoke bed, although the delivery end 8 was so arranged as to avoid any ofthe charging stock being delivered closer than about /3" to the innerwall of the vessel. The vapourous distillate from the reaction vesselwas allowed to pass through the laterally disposed pipe Band wascondensed and collected in the vessel i0, whilst liquid reac tionproducts were removed through the conical end I! and collected in thevessel l2. A pipe l3 was provided for admitting a suitable carrier gasbelow the plate 2, for the purpose of accelerating the withdrawal of thevapourous distillate.

In the apparatus illustrated in Figures 2 and 3 the reaction vessel M,which was of rectangular shape, contained a quantity of lead I5maintained in a molten state by means of a burner I6, the amount of leadbeing such that in the molten state its upper surface was flush with orvery slightly lower than the lower part of a discharge outlet llarranged at one end of the vessel. The cover or lid l8 was arranged toprovide a liquid seal, as at l9 and a shallow space adjustable as to itsdepths, above the surface of the molten lead. A feed pipe 2| wa disposednear the end remote from the outlet IT and a carrier gas pipe 22enabled'a stream of non-oxidising gas to be discharged just above thelevel of the molten lead so as to facilitate rapid removal of allproducts of the reaction. The outlet I! discharged into a two-way pipe,one limb of which 23 was downwardly directed for the passage of liquidproducts, whilst the other limb 24, was upwardly directed and adaptedfor the passageof vapourous distillate to a receiver not shown. A pocket25 for housing a pyrometer was arranged in the vessel 14.

The vessel illustrated in Figures 2 and 3 enabled a higher reactiontemperature to be employed than with the apparatus according to Figure1, as by lowering the lid or cover I8 the velocity of the vapours couldbe increased, thus reducing the risk of decomposition of the liquidconversion products or of cracking the vapours.

In a plant constructed according to Figure 4 the charging stock flowsfrom a charge tank. 26

65 in benzole.

6 gas fired preheater 28, feed. control and vapour trap assemblyindicated generally at 29 to the converter 30. The converter ispreferably of cir- 1 cular shape and comprises a shallow and preferablydished or slightly conical metal bath 3| filled with lead 32 which iskept molten by means of a gas-fired furnace 33. A rotary scraper 34,

for scraping the surface of the lead bath is provided and is driventhrough the gears 35. A centrally disposed cylindrical chamber 36,closed at its lower end and having one or more parts or openings at ornear its upper end serves as an overflow weir for the rapid andcontinuous removal of liquid conversion products which collect in thelower end of the said chamber, through which projects an outlet pipe 31for discharging the said products into a mould or other receiver 38.. Aspreader or shield 39 is so disposed over the open end of the pipe 31 asto leave a clearance space for the passage of the liquid. A gas returnpipe 40, described below is adapted to blow returned vapours through theliquid collected in the bottom of the chamber so as to liberate anyentrained vapours. A spilled lead drawofi pipe 4! ispreferably provided.The vapours are discharged through the pipe 42 and pass through anydesired series of dephlegmators and condensers to a gasometer 43 wherethey are stored for use as fuel or for any other desired purpose. Aseries of draw-01f pipes 44 is provided at convenient points of thedephlegmating and condensing part of the plant, for the purpose ofremoving any heavy distillate which may have collected. At a convenientpoint of the system near the gasometer, we provide an exhauster 45 fordrawing the vapours through the plant, and forcing them into thegasometer. The gas return pipe 40, which is branched off the pipe 42, onsuitable operation of the cocks or other controlling devices indicatedat 46, enables a controlled proportion of the gases and/or vapours to bereturned and blown through the liquid conversion products collected inthe lower end of the chamber 36.

Valve-controlled drain pipe 4! is provided for the drainage from pipe 42of any liquid which may have been entrained in and then deposited fromthe vapors and gases passing through pipe d2.

Examination of products-The examination of the products obtained in allthe undermentioned experiments was carried out as follows:

The distillate and the liquid conversion product (hereinafter referredto as L. C. P.) from the experiment were mixed and treated withpetroleum ether (13. P. 100/120 C.) by mixing them thoroughly at about/80 C. and then allowing them to cool. On standing the mixture separatedinto two layers: '(a) a portion insoluble in petroleum ether, which wasa resin which solidified from the molten stage into a hard shiny blackproduct with a softening point of about 60-80 C. This resin, which inthe examples given below, is referred to as extract 1, was found to besoluble The solution, on application to a smooth surface and on beingallowed to evaporate, yielded an excellent hard shiny brown film whichdried very quickly. In its original form the resin sometimes containedmatter of a more or less 7 coke-like nature, which can be separated byfiltering the benzole solution. It depends on the conditions of the testwhether such carbonaceous matter can be filtered ofi easily andimmediately or, only after some additional treatment such as fitted witha heatingcoil through thepipe 21, standing for some hours. Theinsolublematter dried to a. coke-like residuum and this term is used inthe examples.

(b) Portion soluble in petroleum etheT.-The petroleum ether wasevaporated and the residue extracted with furfural and the two fractionsthus obtained treated separately. Two separate resins were obtained, onefrom the bottom layer (extract 2) and one from the top layer (extract3). The various oils referred to as having been obtained in thefollowing-examples were all obtained by distillation of one or other orthe two fractions resulting from the furfural extraction ofthe solubleportion (1)).

It will of course be obvious that other solvents and/or workingconditions than those described could if desired be used for examiningand working up the conversion products.

Moreover the properties of the extracts vary according to the conditionsof the operation, that is, according to the state of transition whichthe products are allowed to attain. Thus, resinous extracts havingsoftening points which differ from those mentioned in the examples, maybe obtained by varying the charging stock or the treatment, whilst stillfurther variations may be efiected by using difierent solvents and/orconditions of separation.

Extract 1.-This can be obtained as a very hard, highly glossy resingenerally melting between 60 and 80 C. and solidifying without anyimmiscible matter. A film from benzole solution is transparent, hard andshiny, drying within a few minutes (Example -8) The extract willsometimes be found to contain coke-like matter which can be separatedeither by filtering the benzole solution or by separating and removingthe upper layer in the molten stage. The resin will still be hard, lessshiny and somewhat more brittle but the film formed from benzolesolution will still be hard and shiny.

Extract 2.--The resin can be obtained as a hard transparent shiny brownproduct which is not brittle. The film from benzole or petrol ethersolution is hard, shiny and of a brown to yellow colour. If the reactionhas not reached the proper stage, the resin is brittle and becomes soagain if the reaction is carried too far, in which case its proportionis reduced, mainly in favour of lubricating oil.

Extract 3.-This extract always contains a hard and somewhat ductileresin, representing probably a more saturated part of extracts 1 and 2.A film of this resin from benzole solution is less hard and has lessgrip on the surface than that of extracts 1 and 2 and the resinresembles an extract 1 produced from a straight-runresiduum.

While the process i not confined to petroleum hydrocarbons, thefollowing examples were mainly carried out with a residuum from liquidphase cracking, as this product is readily available and represents atpresent a product of very small value. One example is given .for astraight-run product to indicate the influence of the charging stock onthe reaction and another one in which a proportion of pitch tardistillate .is added as representing aromatic compounds.

It seems that hydrocarbons boiling above 300 C. but below the asphalticmatter contribute considerably to the formation of resins or otherproduct-s of large molecular size. The examples given show the influenceof the catalyst. Thecatalyst used wa in all cases in the form of adistillate obtained from a treatment of the metal and residuum asdescribed in'application 'Serial No. 481,923.

'As already stated, other solvents may be used either instead of or inaddition to those already mentioned, for the purpose of effectingextraction or separation, whereby the variety of resinous productsobtainable may be increased; thus, for example, butyl acetate might beused to separate a lighter resin from extract 1.

Example 1.-The apparatus shown in Figure 1 was used and the charge,pre-heated to about 100 C., was dripped on to the coke while the funnelwas slowly turned in order to allow the coke lumps to become almost freefrom the previous charge before a fresh charge could reach them. Thecharging stock used was straight-run residuum from Venezuelan crude,topped to 360 'C., with a specific gravity of 0.98 at 60 F. Thetemperature in the lead bath was 450 C. The rate of feed was 2 gms. perminute. 100 cos. of CO2 per minute were used as carrier gas. The yieldof distillate and L. C. P. was coke 16%, gas and loss 4%, The catalystwas arsenic, one part per 500,000 parts of charge.

Analysis of L. C. P. and distillate Per cent by weight of the chargeExtract 1 (black film from benzole solution not very hard) 10 Extract 2(hard, transparent) 5 Extract 3 (9% representing petroleum jelly) 12Lubricating oil 33 Gas oil (Diesel Index 58) 12 Oil boiling below 230 C5 Coke-like residuum, obtained from insoluble portion (a) by benzoleextraction 3 Example 2.The conditions of the experiment were exactly thesame as in Example 1, but the charge was a residuum from liquid phasecrackins, topped to 340 C. and had a specific gravity of 1.1. The yieldof distillate and L. C. P. was 86%, coke 11%, gas and loss 3%.

Analysis of L. C. P. and distillate Per cent by weight of the chargeExtract 1 (black, hard, film hard, very adherent) 14 Extract 2 (hard,transparent) 39 Extract 3 (2% representing petroleum jelly) 3Lubricating oil 20 Oil boiling below 300" C 1 Coke-like residuum 9Example .3.-The apparatus shown in Figures 2 and 3 was used and thecharge and catalyst were the same as in Example 2. The charge waspre-heated to 225 C., the rate of feed was 10 gmspper minute. Thetemperature of the lead bath was 440/445 C. No carrier gas was used. Theyield of distillate and L. C. P. was 99%, gas and loss 1%.

Analysis of distillate and L. C. P.

Per cent by weight of the charge Extractl (as from ,Example 2) 33Extract :2 (as from Example '2) 38 Extract 3 (Black, fairly hard film) 6Lubricating oil 12 -Oiljboiling below 330 C 4 Coke-like residuum 6Examples 4 and elm-The charge consisted of 9.5% of-topped crackedresiduum and.5% topped straight-run residuum. The conditions employedWere'the same as in Example 3, except that the rate of feed was reducedto'2.5 gms. per minute while Example 4 was carried out with arsenic ascatalyst, no catalyst was employed with Example 4a and in both cases 100ccs. of CO2 per minute were used as carrier gas. The yield ofdistillates and residuum was in both cases 97% and gas and loss 3%.

Analysis of distillate and L. C. P. (all percentages are by weight ofthe original charge) Extract 1 Lubricating oil Oil boiling below 340 0.-Coke-like residuum The extract 1 of Example 4 gave a harder shinier filmfrom benzole solution than extract 1 from 4a. Extract 2 from 4 was hardand shiny, while that from 4a was soft and sticky. Extract 3 from 4contained 3.5% of a good petroleum jelly, while of 95% topped crackedresiduum and 5% topped straight-run residuum (Cumarabo) the catalystconsisting of one part per 200,000 parts of the charge of a mixture ofphosphorus, bismuth and vanadium of equal proportions and prepared inthe form of a distillate as described in application Serial No. 481,923.The apparatus shown in Figures 2 and 3 was used. The rate of feed wasgms. per minute, the temperature in the lead bath being 455/460 C. forExample 5 and 480/485 C. for Example 5a.' No carrier gas was employed.The yield of distillate and L. C. P. was 99% for Example 5 and 98% forExample 5a.

Analysis of distillate and -L. C. P.

Per cent by weight of charge 5 All the products in the desired rangeshowed better qualities from Example 5 than from 5a.

Extract 1.-The extract from Example 5, when directly melted, was a veryhard and shiny resin with almost no top layer of carbonaceous matter.The film from benzole solution was very hard, smooth; shiny andtransparent and stuck firmly to the surface. Similar tests on theproduct from 5a showed a very brittle resin with a considerable toplayer of carbonaceous matter, while the film from benzole solution couldcomparatively easil? be removed from the surface.

Extract 2.The extract from Example 5 was much less brittle than thatfrom 5a.

Extract 3.The extract from Example 5 wasa mixture of a hard and somewhatductile resin 8% and an excellent petroleum jelly 7%. which Yieltd ofliquid phase products and distil- Lubricating oil above 350 C 10 wereseparated as described. No jelly was obtained from 5a.

The lubricating oil from 5 was superior to that from 5a. The parafiinicoil boiling from 360/385 C. contained almost no wax from Example 5,while it was very waxy from Example 5a.

Example 6.-A'Gulf Venezuela crude was treated with furfural and theparafiinic layer topped to 375 C. The residuum was an asphalt, soft atordinary temperature. It was treated in the apparatus shown in Figures 2and 3 (a) as such (b) mixed with 40% of its weight of extract 1 derivedfrom Example 5. (-0) mixed with 40% of its weight of extract 2 derivedfrom Example 5.

Catalyst: Mixture of P, As, Bi, V in equal parts-- 1 part in 200,000parts of the charge.

Rate of feed-3 ccs. per minute.

No carrier gas was used.

Temperature in lead bath 440-445 C.

Yield of L. C. P. and distillate Gas oil Coke-like residuum REMARKS.IIthe case of (a) a separation of the residuum from the petrol etherextraction was not satisfactorily possible and the product dried assuch, when it resembled the coke-like residuum from the previous test.Its proportion is, therefore, given in that column.

' 91% boiled. from 320-400 C. (50% at 360 C.)

Temperature 465 0.

Catalyst: P, As, V in equal parts-1 part taken together in 200,000 partsof the charge.

Rate of feed 3 005. per minute.

No carrier gas was used.

I. B. P.

By weight of charge of extract 1 9 By weight of charge of extract 2 Byweight of charge of extract 3 Oil boiling below 350 C Coke-likeresiduum.

Extract 1 (a) could be molten without separating carbonaceous matter andwas a hard shiny black resin. Extract 1 (b) could not be treated in thesame way but the carbonaceous matter had to be separated. Extracts 2were in both cases of almost the same appearance, medium.

hard, ductile,.brown and transparent- Extracts 3 contained. petroleumjellies in both cases (1.5%

late of the-same stock-with a boiling range as referred to in Example'7. The catalyst consisted of one part in 500,000 parts of the charge ofa mixture of phosphorus, bismuth and vanadium in equal proportions andprepared in the form of a distillate as described in application SerialNo. 481,923. The apparatus shown in Figures 2 and 3 was used. The rateof feed was 5 gms. per minute, the temperature in the lead bath was455/460 F. No carrier gas was employed. The yield of distillate and L.C. P. was 99%.

Analysis of distillate and L. C. P.

Per cent by weight of the charge Extract 1 33 Extract 2 24 Extract 3 7Lubricating oil Oil boiling below 350 C Extract 1 was very hard,exceptionally glossy and not brittle, melting without forming a toplayer of coke-like matter.

Extract 2 was hard and transparent, not brittle. Extract 3 was a mixtureof a hard ductile resin and petroleum jelly (5%).

on boiling below 350 0. contained 0.7% below 200 C. and 2.5% below 300C. Initial boiling point 108 C. Example 8a.The cracked distillate astreated in Example 8 was treated without any admixcharge is too great,some part would remain un- 60 F. of which 43% boiled above 350 C., and0f ggybFof a coal tar pitch distillate sp. gr. 1.215 at The catalyst Wasvanadium (1 part per million) used as described in previous examples.

The temperature was 495-505 C., charge preheated to 180 C.

The lead bath was 15 in. Wide and 12 in. long.

Rate of feed: 4 gallons/hour.

Yield: 97%.

Approx. 87% was recovered in liquid phase, and 10% as a distillate.

In this case both fractions were collected and analysed separately.

Extracts 1,2 and 3..--The.method described for the separationof thematerial referred to as "ex- Cal Cal

converted, and would be obtained with extract 1, in which case themolten product would not be homogeneous. When such a product is allowedto cool, two layers are clearly visible, the top layer having a verybrittle and almost coke-like appearance, whilst the lower layer clearlyappears to have been molten.

To avoid the presence of unconverted asphaltenes the charge may ifnecessary be blended with a proportion of a charge containing lessasphaltic matter (Example 8) or some parafiines may be added, or theconditions of the reaction may be made more severe, e. g. by increasingthe temperature and/or contact time or a combination of these methodsmay be applied.

Extract 2 is in some ways similar to a resin which is known to occur inasphaltic products and which can be obtained from it by the same processof extraction as described in this application for extract 2.

Although it may be that a part of extract 2 is derived from such a resinit is not necessarily so for all of it as shown in Example 71).

While the original resin in the asphalti matter was very brittle evenwhen oil was only removed to a maximum boiling temperature of about 345C. the extracts 2 showed a different behaviour and could be obtained asa ductile, clear,

transparent and shiny resin even when oil was taken oil to 375 C. andhigher. lubricating or drying oils.

Extracts 3 show the greatest variation. It may be that they are formed,at any rate to some extent, by further conversion of extracts l and 2,so that extracts 3 obtained by the method as described herein, and whichare not jellies, but resins, might be the more parafiinic parts ofextracts 1 and 2 which have become immiscible with furfural.

Some of these products occur with the jelly and can be separated bytopping the parafiinic layer from furfural treatment to about 370- 400C. dissolving the residuum in petrol ether and filtering oil theinsoluble resin. The filtrate is treated with acid and the clearfiltrate freed from the ether, when the jelly remains.

It should be noted that in every case the substances produced accordingto the invention are different from those which would be produced by anordinary distillation. The reaction which occurs according to theinvention appears to consist in part of a distillation and in part of a,conversion which takes place in liquid phase, and the process maytherefore be described as one of convertive distillation, which termcould also appropriately be used to describe the reactions which formthe subjects of my said earlier applications. Inasmuch as the reactionproduces a minimum amount of gas and low boiling hydrocarbons, the bulkof the products obtained being more saturated than the charging stock,the process can in no sense be regarded as a cracking process, or as oneof destructive distillation inv which large proportions of. coke, gasand lowboiling. hydrocarbons are formed.

The invention is not limited to use with residua,

Such oils are 13 but heavy distillates will be found t undergo a similarconversion, with formation of products different from those contained inthe charge, whilst a considerable part of the products recoverable willbe found to have good lubricating properties or to be useful as dryingoils.

The reaction can be carried out under reduced, normal or increasedpressure and it should be noted that the relation between the volume ofthe distillate and converted products, as Well as their properties canbe Widely varied by suitably vary ing one or more of the reactionconditions such as the catalyst, the rate of feed, temperature, andnature and heat capacity or the contact surface according to thecharging stock to be used.

Moreover it may be found that some mixtures of hydrocarbons, aftertreatment Will contain resinous products which are softer or harder thanindicated in the examples, and even the order of softening points may bedifierent: e. g. an extract 2 might be harder than an extract 1.

I claim:

A process for the conversion of heavy hydrocarbon liquid having aboiling point of at least 14 350 C. and containing a substantialproportion of unsaturated compounds into valuable hydrocarbons of highmolecular weight and mainly of a more saturated nature than said heavyhydrocarbon liquid, said process comprising maintaining in a reactionzone for said heavy hydrocarbon liquid a molten surface at a temperatureof from about 430 C. to about 500 0., distributing said heavyhydrocarbon liquid over the molten surface at a controlled rate of feedsuch that each particle of the liquid is rapidly raised to a temperatureat which it is partially vaporized and the unvaporized portion thereofremains in liquid condition, immediately removing the resultant vaporousand liquid conversion products from the zone of reaction before anysubstantial cokin of the liquid occurs, said process being furthercharacterized in that the said heavy hydrocarbon liquid is one yieldinga resinous material in the liquid conversion products, and said liquidconversion products are subjected to a solvent extraction to separatesaid resinous material therefrom.

EMIL HENE.

